Polyolefin emulsions containing n,n-dimethylsulfenyl dithiocarbamates

ABSTRACT

Stable oil-in-water emulsions of N,N-dimethyl alkylsulfenyl dithiocarbamates rodent repellents with polyolefins are prepared using emulsifying agents selected from amphoteric, nonionic, cationic, and anionic emulsifiers, which emulsions can be readily applied to surfaces to render same rodent and roach repellent. If desired, the polyolefin emulsions can be blended with asphalt and asphalt emulsions prior to application to a substrate.

as: ana ram kill m "7 United State:

oodrutf June 19, 1973 POLYOLEFIN EMULSIONS CONTAINING N,N-DIMETHYLSULFENYL DITHIOCARBAMATES Gene N. Woodruff, Bartlesville,Okla.

Assignee: Phillips Petroleum Company Filed: Apr. 30, 1971 Appl. No.:139,242

Related US. Application Data Continuation-impart of Ser. No. 760,706,Sept. 18, 1968, Pat. No. 3,615,798.

Inventor:

US. Cl 260/29.7 M, 106/15 AF, 106/271,

106/272, 260/29.7 SO, 260/29.7 EM, 424/27, 7 1 424/30, 424/325 Int. Cl.co'sd 7/00, 009d 5/02 Field of Search l06/l5 AF, 272;

260/28, 28.5 R, 29.6 MM, 29.6 MO, 29.6

MN, 28.5 A, 29.7 M, 29.7 SQ, 29.7 NQ, 29.7 SE, 29.7 EM; 424/27, 30, 325

[56] References Cited UNITED STATES PATENTS 2,862,850 l2/l958 Goodhuel67/46 3,351,495 11/1967 Larsen et al... 136/146 3,426,133 2/ 1969Shotton 424/30 X 3,429,841 2/1969 Pollock et al.. 106/271 X 3,579,4615/1971 Glaub lO6/27l X Primary Examiner.l0an B. Evans Attorney-Young &Quigg [57] ABSTRACT 6 Claims, No Drawings BACKGROUND OF THE INVENTIONThis application isa continuation-in-part application of copending Ser.No. 760,706, filed Sept. 18, 1968, entitled Asphalt Emulsions, now US.Pat. No.

The present invention relates to coating compositions and to theirpreparation. In accordance with another aspect, this invention relatesto stable oil-in-water polyolefin emulsions containing rodent and roachrepellents. In accordance with a further aspect, this invention relatesto stable oil-in-water emulsions of N,N- dimethyl alkylsulfenyldithiocarbamates with a polyolefin prepared with at least oneamphoteric, nonionic, cationic, or anionic emulsifying agent. Inaccordance with a still further aspect, this invention relates to afabric prepared from fibers of a polyolefin coated with an oil-in-waterpolyolefin emulsion of the invention. In accordance with another aspect,this invention relates to stable oil-in-water polyolefin emulsionscontaining a rodent and roach repellent and asphalt.

The problem of attack of growing trees and other nursery stock, as wellas certain plants, by rodents, particularly rabbits, has become seriousin many localities.

' In many instances the problem is also serious in buildings which areused for storage of various grain products. Any material which has arepellent action toward rodents, including rabbits, rats, etc., andwhich can be.

readily applied to surfaces to be protected would be highly useful andadvantageous when applied to objects which are subject to attack byrodents.

In accordance with the invention, polyolefin emulsions containing arodent and roach repellent are provided, which emulsions are readilyapplied to surfaces for rodent and roach proofing various facilitiesutilizing these surfaces. treated with emulsions of the invention.

Accordingly, an object of this invention is to provide stableoil-in-water polyolefin emulsions.

Another object of this invention is to provide stable oil-in-wateremulsions of polyethylene containing rodent repellent.

A further object of this invention is to provide a cloth or mat-offibers of polyolefin coated with polyolefinic emulsions.

A still further object of this invention is to provide oil-in-waterasphalt-polyolefin emulsion blends;

"A further object of this invention is to provide stable polyolefinemulsions containing rodent repellent in the form of an emulsion ofrodent repellant and asphalt.

Other aspects, objects and the several advantages of this invention willbe readily apparent to those skilled in the art upon reference to thefollowing description and appended claims.

SUMMARY OF THE INVENTION According to the invention, blends of at leastone N,N-dimethyl alkylsulfenyl dithiocarbamate and an oilin-waterpolyolefin emulsion comprising polyolefin, water and selectedemulsifying agents are provided.

The polyolefin emulsions can be amphoteric, anionic, cationic, ornonionic and can be prepared by any method suitable and known to thoseskilled in the art.

Further, in accordance with the invention, it has been found thatpolyolefins, particularly polymers of monol-olefins having from two toeight carbon atoms per molecule, preferably polymers of ethylene orpropylene, including both homopolymers and copolymers, after heatingwith rodent and roach repellent, can be emulsified with at least one ofsaid emulsifying agents. The resulting composition of dithiocarbamateand polyolefin can be applied to surfaces for protecting same againstattack by rodents and roaches.

In accordance with one embodiment of the invention, a cloth which isimpervious to water is prepared from the fibers of a polyolefin and iscoated or impregnated with oil-in-water emulsions prepared from apolyolefin, water, and selected emulsifying agents and an N,N-dimethylalkylsulfenyl dithiocarbamate, a rodent and roach repellent.

In accordance with a further embodiment of the invention, stableoil-in-water emulsions comprising (a) an N,N-dimethyl alkylsulfenyldithiocarbamate; (b) polyolefin and at least one emulsifying agentselected from (1) amphoteric, (2) nonionic, (3) anionic, and (4)cationic emulsifying agents are prepared, which emulsions can be appliedto surfaces desired to be rendered rodent and roach repellent.

It has also been found, as set forth in said copending application, thatthe polyolefin emulsions can be blended with an asphalt emulsion beforeapplying to a substrate. 7

In accordance with an embodiment of the invention as set forth in saidcopending application, the N,N- dimethyl alkylsulfenyl dithiocarbamateis incorporated into the asphalt emulsion by emulsifying thedithiocarbamate with a polyolefin prior to blending with the asphaltemulsion. The resulting emulsions are excellent rodent repellentcompositions' DESCRIPTION OF PREFERRED EMBODIMENTS In accordance withthe invention, it has been found that stable emulsions of polyolefins,particularly polymers of mono-l-olefins having from two to eight carbonatoms per molecule, preferably polymers of ethylene or propylene,including both homopolymers and copolymers, can be prepared with certaindithiocarbamates such as herein described. Polyolefins presentlypreferred are polyethylenes having molecular weights less than 100,000and a melt index of at least about 90.

It has been further found that the dithiocarbamates described herein canbe effectively incorporated into an asphalt emulsion by firstemulsifying the dithiocarbamate with a polyolefin such as polyethyleneand/or polypropylene. The amount of polyolefin emulsion blended withasphalt emulsion will generally be up to about 20 weight percent oftotal blend, preferably in the range 1-10 weight percent in the totalblend. The

resulting compositions containing dithiocarbamate and polyolefin and,optionally, asphalt have been found to v be excellent rodent repellentcompositions which can be readily applied to surfaces for protectingsame against attack by rodents.

bamate compounds can be found in U.S. Pat. No. 2,390,713 and U.S. Pat.No. 2,862,850.

The amount of dithiocarbamate present in the emulsions of the inventionset forth in more detail hereinbelow range from 0.5 weight percent to 20weight percent, preferably 1 to 10 weight percent.

The amount of polyolefin present in the emulsions of the invention canvary appreciably, but will generally be in the range of 1 to 20 weightpercent, but for some emulsions, the amount of polyolefin can range upto 25 weight percent or higher. The amount of emulsifier present canrange from 0.1 to about 5 weight percent, but in some instances can beas much as weight percent or more, if desired. The balance of theemulsion comprises water which will ordinarily amount to 80 to 99 weightpercent based on the total blend.

As indicated above, the emulsions of the invention are particularlyeffective as coating or impregnating compositions to be utilized inplaces where it is desired to protect surfaces against attack byrodents. However, if desired, the compositions of the invention can beused for other applications, including water-proofing material for roofsand the like, for covering spaced-insurfaces in irrigation canals,ponds, open dams, and the like, and for related uses. The impregnatedcloth or matting can be used for either temporary or permanent roofing,for mulching, for tenting material, and for related uses.

In accordance with a further embodiment of the invention, the polyolefinemulsions or blends of asphalt and polyolefin emulsions can be appliedto a cloth or mat made from fibers, for example, fibers formed fromsynthetic thermoplastics, such as polypropylene fabric, that have beenpreviously woven or matted into a cloth or structure resembling same toform a water-proof structure. The water in the emulsion can be removedby any suitable method such as air drying or drying in an oven or byother heat.

It is also within the scope of the invention to add short fiber asbestosand similar materials to the emulsions of the invention. The addition ofshort fiber asbestos, for example, to the emulsions of the inventionincreases the usefulness of the emulsions, increases the viscosity andpermits application of the emulsions to surfaces where improved adhesionis necessary. The ring and ball properties of the dried product whenasphalt is present is greatly increased by the addition of asbestos. Theamount of asbestos added can be varied depending on the resultingdesired characteristics, but in general will be in the range of 1 to 10weight percent. The asbestos fibers are finely divided and ordinarily0.1mm to 2.0mm in length.

The asphalts that can be used'in the preparation of the emulsions thatcan be blended with the polyolefin emulsions include any of thosebituminous materials used heretofore and known in the prior art such asnatural asphalts or those derived from petroleum refining, for example,by steam refining and/or air blowing, and the like. Asphaltscharacterized by penetrations (ASTM D-5-5 1) from 0 to about 300, oreven higher, and preferably from about 40 to 300, and having softeningpoints (ASTM D36-26) in the range of 90 to 250 F, and preferably 100 to150 F, represent suitable asphalts that can be employed.

The relative amounts of the various components of the asphalt emulsionswhich can be blended with the polyolefin emulsions can vary, but ingeneral the asphalt is present in an amount in the range of 50 to 90,preferably 60 to weight percent; the emulsifier is present in an amountin the range of 0.1 to 4, preferably 0.25 ml; and water is present in anamount between 50 and 10 Weight percent based on the total blend.

The asphalt emulsions employed can be prepared by any method known tothose skilled in the art, for example, by preparing a soap solutioncomprising water, either soft or hard, and an emulsifying agent, eitheramphoteric, anionic or nonionic. The soap solution is then mixed in acolloid mill or the like with the asphalt phase, the latter beingpreferably heated to reduce the viscosity. Usually, the emulsifiers andany modifiers or promoters are dispersed in the water to form a soapsolution which is then warmed to a temperature of to 200 F, preferably90 to F. The asphalt can be heated to a temperature in the range of to350 F, preferably 250 F to 300 F. The warm soap solution and hot asphaltare then proportioned to a colloid mill to emulsify the mixture, duringwhich milling the temperature of the mixture can be in the range of 100to 210 F, preferably 150 to 200 F. The completed emulsion is then cooledto a temperature below 150 F before being used or transferred tostorage. The method of preparing an emulsion will have some effect onthe properties thereof and the intended application or utility of theemulsion will dictate which particular method one should use to get thedesired properties.

The asphalts described above can be emulsified as set forth in saidcopending application with amphoteric, nonionic, and anionic emulsifyingagents.

As indicated previously, the emulsifying agents employed to prepare thepolyolefin emulsions of the invention can be amphoteric, anionic,cationic, or nonionic, or combinations thereof.

One useful emulsifying system is oleic acid and triethanol amine.

Amphoteric emulsifying agents that can be used include the betainederivatives such as coco betaine (Culveram CDG) and cetyl betaine (BCO),as well as other cocoand tallow-derived glycinecompounds, stearylammonium sulfonic acid betain, myristyl ammonium sulfonic acid betain,polyoxyethylated amine derivatives, and the like.

Emulsifying agents containing both amino and carbonyl groups can be usedsuch as those emulsifying agents having the formula wherein R is analiphatic hydrocarbon radical containing four to 25 carbon atoms.

Nonionic emulsifying agents which are effective are those containing 20to 60 ethylene oxide groups, for example, Triton X-lOO, Triton X-305,and Triton X-405.

Anionic emulsifying agents which are effective include Vinsol resin,with or without lndulin C, as well as sodium salts of stearic acid,oleic acid, linoleic acid, saturated acids, tall oil derived anionicemulsifiers, and the like.

One preferred procedure for obtaining a cationic emulsion is to employan acid with suitable emulsifyingpyleneoxy)nonadeca(ethyleneoxy)ethanol,

agents to form an emulsion having an acid pH below 7. In preparing thecationic polyolefin emulsion, 'an emulsifying agent from the classes ofnonionic or amphoteric is added to an aqueous polyolefin mixture and anacid, such as hydrochloric acid, sulfuric acid, acetic acid, or sulfamicacid, can be incorporated into the mixture to impart an acid pH below 7to the emulsion. Generally, pl-ls in the range of l to about 10,preferably 2 to 4, are suitable for these acidic emulsions. The amountof the acid will generally be 0.1 to 1.5, preferably 0.3 to 0.8 weightpercent of the emulsion, but can be considered and calculated as part ofthe emulsifying agents.

Cationic emulsifiers are also effective for producing stableoil-in-water emulsions according to the invention.

Additional suitable nonionic emulsification agents include those of thegeneral formula:

( JHa where R is selected from the group consisting of hydrogen, aryl,and alkylaryl radicals; and x, y and z are integers, such that (1) whenx is 0, y is also 0, z is in the range of 6 to 1 1, inclusive, and saidR is one of said aryl and alkylaryl radicals, and (2) when x and y areeach greater than 0, the sum of x and z is in the range of to 40,inclusive, and y is in the range of to 60, inclusrve.

Representative examples of the nonionic emulsifying agents include:phenoxypenta(ethyleneoxy)ethanol,

-phenoxyocta(ethyleneoxy )ethanol, phenoxyennea( ethyleneoxy)ethanol,phenoxydeca(ethyleneoxy)ethanol,4-methylphenoxypenta-(ethyleneoxy)ethanol,2,3,6-triethylphenoxyhepta(ethyleneoxy)ethanol, 4( l l,3,3-tetramethylbutyl )phenoxyhepta( ethyleneoxy )ethanol, 4(1,3,5-trimethylhexyl)phe noxyhexa(ethyleneoxy)ethanol,4-nonylphenoxyhepta(ethyle'neoxy)-ethanol,2,3,4,5,6-penta-npentylphenoxyennea(ethyleneoxy )ethanol, 2(1 ,3,5-trimethylhexyl )-4( 1 ,3-dimethylbutyl)phenoxypenta(ethyleneoxy)ethanol,4(3,5,5- trimethylheptyl)phenoxyhexa(ethyleneoxy)ethanol,

3 3 ,5 ,7,7-trimethyl-trimethyl-5- ethylnonyl)phenoxyhepta(ethyleneoxy)ethanol, 4( 1,1-,3,3,5,5,7,7-octamethyldecyl)phenoxyennea(ethyleneoxy)ethanol,4-n-pentacosylphenoxypenta(ethyleneoxy)ethanol,3,5-di-n-decyl-4-n-pentylphenoxydeca( ethyleneoxy)ethanol,betahydroxyethyleneoxytetraconta(propyleneoxy)octadeca(ethyleneoxy)ethanol, betahydroxymethoxyoctadeca( ethyleneoxy)tetracontra( propyleneoxy )ethanol beta- 'hydroxyethoxyennea(ethyleneoxy )pentaconta(propyleneoxy )deca(ethyleneoxy ethanol,betahydroxyethoxynonadeca(ethyleneoxy)hexaconta(probetahydroxyethoxytetradeca(ethyleneoxy )pentatetraconta(propyleneoxy)tetradeca(ethyleneoxy)ethanol,phenoxyethyleneoxypentapentaconta( propyleneoxy )octatriaconta(ethyleneoxy )ethanol, 4- methylphenoxydeca(ethyleneoxy)nonatetraconta(propyleneoxy)eicosa(ethyleneoxy )-ethanol, 4( l ,3 ,5-trimethylhexyl)phenoxyhexa(ethyleneoxy )pentacontra(propyleneoxy)triconta(ethyleneoxy)ethanol,4-npentacosylphenoxypentacosa(ethyleneoxy)-pentaconta(propyleneoxy)deca(ethyleneoxy)ethanol,2,4,5-trimethylphenoxydeca-(ethyleneoxy)pentaconta(propyleneoxy)pentacosa( ethyleneoxy)ethanol, 2(l,3,5 -trimethylhexyl)- 4( 1 ,l ,3,3-tetramethylbutyl)-phenoxyeicosa(ethyleneoxy)hexatetrac0nta(propylenwhere R is selectedfrom the group consisting of hydrogen, aryl and alkaryl radicals; and x,y, and z are integers such that (1) when x is O, y is also 0, z is inthe range of 20 to 60, and R is one of said aryl and alkaryl radicals,and (2) when x and 'y are each greater than 0, the sum of x and z is inthe range of 50 to 350, and y is in the range of 40 to 60.

The nonionic emulsifying agents, as shown by the general formula,represent a rather narrow class of compounds and they have a criticalbalance of hydro-,

phobic component "(the R and propyleneoxy groups) and hydrophiliccomponent (ethyleneoxy groups) necessary to give the necessary mixingtime. Within the general formula given earlier for thesenonionicemulsifying agents, there are two referred subclasses that canbe represented by the following general formulas:

where R, is selected from the group consisting of hydrogen and alkylradicals having one to 25 carbon atoms, the total number of carbon atomsin the alkyl radicals preferably does not exceed 25, and n is an integerin the range of 20 to 60; and

where a and c are integers greatervthan 0 and whose sum is in the rangeof 50 to 350, b is an integer in the.

range of 40 to 60, and R is selected from the group consisting ofhydrogen and the hydrocarbon radical:-

Suitable anionic emulsifying agents employed include the sulfonates,particularly the alkylaryl sulfonates, such as: p-dodecylbenzene sodiumsulfate, nor iso-p-octylphenoxypoly(ethyleneoxy)ethanol sodiumsulfonates, sodium isopropylnaphthalene sulfonate, sodiumtetrahydronaphthalene sulfonate, and methylnaphthylene sodium sulfonate(Petro Ag); and the sulfates: sodium cetyl sulfate (n-hexadecylsodiumsulfate), ammonium lauryl sulfate, sodium tridecyl sulfate; and thephosphates: allgylpolyphosphates, complex amidophospho salts, aswlfases't'fs an d bthers such as: sodium diamyl sulfosuccinate anddisodium-N- octadecyl sulfosuccinamate.

EXAMPLE I Runs were carried out in which tert-butylsulfenyldimethyldithiocarbamate was emulsified with polyethylene and subsequentlyblended with an asphalt emulsion.

In one run, 7 grams of tert-butylsulfenyldimethyl dithiocarbamate, 38grams of polyethylene, 8.6 grams oleic acid, and 6.7 grams of triethanolamine were melted together at a temperature of 270 F and were pouredslowly into 302 grams of water at a temperature of 200 F with constantstirring by a dispersator at a high speed. The stable polyethyleneemulsion thus formed can be used as such as rodent repellent or roachrepellent. If desired, the substrate can be applied to a substrate suchas polyolefin fabric. The polyethylene emulsion is colorless and willstick to solid surfaces and fabrics.

In another run, the resulting stable polyethylene emulsion was blendedin an amount of 10 grams with 12 grams of an asphalt emulsion usingcetyl betaine as the emulsifying agent. The resulting blend producedupon drying a product containing 2 percent tert-butylsulfenyldimethyldithiocarbamate, 82 percent asphalt, and l 1.3 percent polyethylene.

The emulsion blend produced above containing the polyethylene, asphaltand dithiocarbamate has also been found to be rodent repellent.

EXAMPLE 11 Additional runs were carried out in whichtert-butylsulfenyldimethyl dithiocarbamate was emulsified withpolyethylene with either a nonionic or a cationic emulsifying system.

In run 1, 0.85 g NaOH and 13.9 g Triton X100(is0- octyl phenylpolyethoxy ethanol with 9-10 oxyethylene groups) were added to 250 ml HO. A blend of 1.82 weight percent R55 (tert-butylsulfenyldimethyldithiocarbamate) in polyethylene was prepared by melting at 265 F and12.8 g of this plastic melt was poured slowly into the 190 F aqueoussolution stirred by dispersator. A stable emulsion resulted. Thecompositions of the emulsions are shown in the following table.

In run 3,2.5 ml 0.51 N I-ICl (containing 0.046 g anhydrous HCl) and 13.1g Redicote E-ll (a polyoxyethylated amine derivative) were added to 250ml H O, heated to 200 F and stirred by means of a dispersator, and 18.4g of a melt containing 0.6 weight percent R55 in polyethylene was addedat 270 F to the stirring aqueous solution. A stable emulsion resulted.The compositions of the emulsions are shown in the following table.

Runs 2, 4, 5, and 6 were similarly prepared (see quantities ofcomponents listed in Table 1 below).

These specific nonionic type emulsions employed in the example cancontain up to about 10 weight percent polyethylene. These specificcationic type emulsions employed in the example can contain up to about25 weight percent polyethylene.

A polyolefin fabric coated with the emulsion of run 1 of Table I andwrapped around the trunk of a young pecan tree protects the tree fromrabbits.

TABLE I EMULSIFICATION OF POLYETl-IYLENE CONTAINING R55 RODENT REPELLENTEmulsion Type Nonionic Cationic Emulsify Agent Triton X-lOO RedicoteE-ll Run No. l 2 3 4 5 6 g Emulsifier 13.9 15.0 13.1 9.4 12.0 11.6 gKOl-l or NaOH (NaOH) (KOH) 0.85 0.9 g Anhydrous HCl 0.046 0.03 0.0460.046 g Polyethylene 12.5 27.3 18.3 40.4 42.8 56.9 g R55 RodentRepellent 0.23 0.165 0.11 0.75 0.26 0.34 ml 11,0 250 250 250 250 250 250F Melt F) 265 275 270 260 260 260 F Aque ous soln. 190 200 190 200 200Emulsion Stable Stable Stable Stable Stable Stable R55 in residue (bywt.) 0.84 0.38 0.35 1.5 0.47 0.49 Plastic in emulsion (by wt.) 4.5 9.36.5 13.5 14.0 18.0 Emulsifier (by wt.) 5.3 5.3 4.7 3.1 4.0 3.7 g isgrams As indicated previously, the emulsions of the invention can beapplied to fabrics or cloth-like materials formed from polyolefins.Thus, the dithiocarbamatepolyethylene emulsion ordithiocarbamate-asphaltpolyethylene emulsion obtained above can beapplied to, say, polypropylene cloth to prevent rodent damage in largegrain storage bins in countries short of food. In some instances, it maybe desirable also to add a thin layer of thedithiocarbamate-polyethylene emulsion to asphalt-polypropylene clothbins already constructed.

Cockroaches, water bugs and other small insects tend to gather and livewhere moist conditions prevail. Asphalt and polyethylene emulsionscontaining dithiocarbamates prevent cockroaches from occupying thesemoist areas when the surfaces are sprayed with the dithiocarbamateemulsions. Painting or spraying the boards on the under side of theframe house discourages the presence of insects. The foundations can bemade repugnant to insects by a coating of thedithiocarbamates-containing emulsions. Cracks in the foundation, inwalls, between wood, or between concrete and wood can be sealed andinsect growth eliminated by the dithiocarbamate emulsions. Growth ofinsects in storage areas of ships can be controlled by the use ofdithiocarbamate emulsions at cracks and corners, on beams, betweenflooring and in every crack and cranny of the vessel where insectsthrive. The cost of fumigation would be saved and the life of woodentimbers increased.

Painting or spraying the ground around the house prevents the passage ofcockroaches and small insects such as termites. Treatment of all woodin, on or near the ground prevents termite attack on the wood. Asphaltand polyethylene emulsions containing dithiocarbamates adhere well toall solids and have a long life since the life of the dithiocarbamatesis the life of the polyethylene or asphalt itself. Any particle ofasphalt or polyethylene is effective because the dithiocarbamates areintimately blended with the carrier asphalt or polyethylene. At times itis desirable to prevent insect growth in a bulk area such as postholes,reservoirs, pits, and depressions. Dithiocarbamate emulsions can be usedto coat sand or gravel, which, as a filler for the hole or pit, wouldnot only prevent insect growth but would seal the entire areawatertight. In such use the pellent and polyethylene emulsionscontaining roach repellent, along with asphalt and polyethyleneemulsions containing no repellent as control runs, were evaluated forcockroach repellency. The method of determining cockroach repellency isthe corner card method. (The corner card is used to determine thepotential repellency of materials treated with the indicated candidatechemical.)

The method is based upon the tendency of cockroaches to congregate inand climb on corner surfaces. The test cards at the dosages and theuntreated control card are placed upright in corner position against theinside wall of a glass box containing German cockro aches (Blattellagermanica). Food and water are placed in the center of the box, andfeeding is permitted ad lib. At hourly intervals a number count is madeof the cockroaches present on each of the cards, as given in Table II.

iiiaiiirf oookiolon 'REP'ELIVJNG rim polyethylene-dithiocarbamateemulsions. A thin layer of the dithiocarbamate emulsions reduces thesmall insects in garbage pails. Use of the emulsions in the corners ofhog sheds and pig troughs helps maintain cleanliness by cutting down thecockroach population. The absence of small insects also helps to preventdisease in the animals.

Treatment of the corners and inaccessible areas of restaurants andgrocery stores helps to keep the premises free of cockroaches, which ismost essential where food is handled. in this case there is no danger offood contamination since the dithiocarbamate is an integral part of theplastic or asphalt.

' EXAMPLE Ill 1 (b) is polyethylene.

Average. Ilours Total Average expressed count of all count per aspercent. I 1 2 3 4 5 6 7 8 0 readings reading of control 5.0% H55 (drybasis) asphalt emulsion 3 1 1 0 1 0 0 0 2 8 0. 0 3.1 0.85% R55 (drybasis) asphalt emulsion 8 4 3 3 3 3 3 6 6 30 4. 3 14. 8 Zero R55(Control) asphalt emulsion"; 20 4 16 12 15 12 29 64 60 261 29.0 100.011.6% R55 (dry basis) polyethylene emulsion... 1 2 3 2 4 2 3 2 1 2.2 4.6 Zero R55 (Control) polyethylene emulsion 47 30 47 54 65 40 51 37 42431 47.9 100.0

NOTE.- R55 tert-butylsulfenyldimethyl dithiocarbamate.

sand, gravel, or even dirt itself, can be pretreated, I claim: dried,and tamped in place. The life of telephone poles 30 l. A stableoil-in-water emulsion consisting essenand posts is increased-by fillingthe hole with pretreated tially of: sand, .dirt or gravel treated by thedithiocarbamatea. 0.5 to 20 weight percent of an N,N- asphalt orpolyethylene emulsions and dried. The presdimethylsulfenyldithiocarbamate compound seence of insects in bomb shelters and falloutshelters is lected from the group consisting of N,N-dimethyleffectivelydiscouraged by treating corners, moist ar- S-methylsulfenyldithiocarbamate and N,N- eas, beams, cracks, and storage areas with thedithiodimethyl-S-tert-butylsulfonyl dithiocarbamate, carbamateemulsions. b. 1 to 20 weight percent of a polyolefin which is a It isdesirable to maintain poultry houses free of polymer of a mono-2-olefinhaving from two to cockroaches, especially in damp corners or storageareight carbon atoms per molecule, eas. Treatment of the corners,cracks,.found ation (and 40 c. 0.1 to about 5 weight percent of anemulsifying its juncture with the wooden beams) will discourage or agentselected from amphoteric, nonionic, anionic, eliminate cockroaches. andcationic agents, and

The kennels of pets and the working areas of veterid. the balance water.nary hospitals are much freer of small insects when the 2. A compositionaccording to claim 1 wherein (a) is corners and moist areas are treatedby asphalt. or N,N-dimethyl-S-tert-butylsulfenyl dithiocarbamate and 3.A composition according to claim 2 wherein (c) is oleic acid andtriethanolamine.

4. A composition according to claim 2 wherein (c) is isooctyl phenylpolyethoxy ethanol with 9-10 oxyethylene groups.

5. A composition according to claim 2 wherein (c) is a cationic systemcomprising a polyoxyethylated amine derivative and an acid.

6. Astable oil-in-water emulsion according to claim 1 wherein (C) is acationic emulsifying system consisting essentially of the reactionproduct of a nonionic or amphoteric emulsifying agent and an acid, theamount of acid present being sufficient to impart a pH below 7 to theemulsion.

2. A composition according to claim 1 wherein (a) isN,N-dimethyl-S-tert-butylsulfenyl dithiocarbamate and (b) ispolyethylene.
 3. A composition according to claim 2 wherein (c) is oleicacid and triethanolamine.
 4. A composition according to claim 2 wherein(c) is isooctyl phenyl polyethoxy ethanol with 9-10 oxyethylene groups.5. A composition according to claim 2 wherein (c) is a cationic systemcomprising a polyoxyethylated amine derivative and an acid.
 6. Astableoil-in-water emulsion according to claim 1 wherein (C) is a cationicemulsifying system consisting essentially of the reaction product of anonionic or amphoteric emulsifying agent and an acid, the amount of acidpresent being sufficient to impart a pH below 7 to the emulsion.